Beruflich Dokumente
Kultur Dokumente
Review
Department of Chemical and Biochemical Engineering, Technical University of Denmark, Sltofts Plads, Building 229, DK-2800 Lyngby, Denmark
Institute of Chemical Technology and Polymer Science, Karlsruhe Institute of Technology (KIT), Engesserstrasse 20, D-79131 Karlsruhe, Denmark
c
Haldor Tops A/S, Nymllevej 55, DK-2800 Lyngby, Denmark
b
a r t i c l e
i n f o
Article history:
Received 13 May 2011
Received in revised form 30 August 2011
Accepted 31 August 2011
Available online 7 September 2011
Keywords:
Bio-oil
Biocrudeoil
Biofuels
Catalyst
HDO
Hydrodeoxygenation
Pyrolysis oil
Synthetic fuels
Zeolite cracking
a b s t r a c t
As the oil reserves are depleting the need of an alternative fuel source is becoming increasingly apparent.
One prospective method for producing fuels in the future is conversion of biomass into bio-oil and then
upgrading the bio-oil over a catalyst, this method is the focus of this review article. Bio-oil production can
be facilitated through ash pyrolysis, which has been identied as one of the most feasible routes. The biooil has a high oxygen content and therefore low stability over time and a low heating value. Upgrading
is desirable to remove the oxygen and in this way make it resemble crude oil. Two general routes for
bio-oil upgrading have been considered: hydrodeoxygenation (HDO) and zeolite cracking. HDO is a high
pressure operation where hydrogen is used to exclude oxygen from the bio-oil, giving a high grade oil
product equivalent to crude oil. Catalysts for the reaction are traditional hydrodesulphurization (HDS)
catalysts, such as CoMoS2 /Al2 O3 , or metal catalysts, as for example Pd/C. However, catalyst lifetimes of
much more than 200 h have not been achieved with any current catalyst due to carbon deposition. Zeolite
cracking is an alternative path, where zeolites, e.g. HZSM-5, are used as catalysts for the deoxygenation
reaction. In these systems hydrogen is not a requirement, so operation is performed at atmospheric
pressure. However, extensive carbon deposition results in very short catalyst lifetimes. Furthermore a
general restriction in the hydrogen content of the bio-oil results in a low H/C ratio of the oil product as no
additional hydrogen is supplied. Overall, oil from zeolite cracking is of a low grade, with heating values
approximately 25% lower than that of crude oil. Of the two mentioned routes, HDO appears to have the
best potential, as zeolite cracking cannot produce fuels of acceptable grade for the current infrastructure.
HDO is evaluated as being a path to fuels in a grade and at a price equivalent to present fossil fuels,
but several tasks still have to be addressed within this process. Catalyst development, understanding
of the carbon forming mechanisms, understanding of the kinetics, elucidation of sulphur as a source of
deactivation, evaluation of the requirement for high pressure, and sustainable sources for hydrogen are
all areas which have to be elucidated before commercialisation of the process.
2011 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
4.
5.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Bio-oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Bio-oil upgradinggeneral considerations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Hydrodeoxygenation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.
Catalysts and reaction mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.1.
Sulphide/oxide catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.2.
Transition metal catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1.3.
Supports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2.
Kinetic models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3.
Deactivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Zeolite cracking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.1.
Catalysts and reaction mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corresponding author. Tel.: +45 4525 2841; fax: +45 4588 2258.
E-mail address: aj@kt.dtu.dk (A.D. Jensen).
0926-860X/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2011.08.046
2
2
3
4
6
6
7
8
9
9
10
10
6.
7.
8.
9.
5.2.
Kinetic models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3.
Deactivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
General aspects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Prospect of catalytic bio-oil upgrading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion and future tasks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
Energy consumption has never been higher worldwide than it is
today, due to our way of living and the general fact that the Worlds
population is increasing [1,2]. One of the main elds of energy consumption is the transportation sector, constituting about one fth
of the total [3]. As the Worlds population grows and means of transportation becomes more readily available, it is unavoidable that the
need for fuels will become larger in the future [4]. This requirement
constitutes one of the major challenges of the near future, as present
fuels primarily are produced from crude oil and these reserves are
depleting [5].
Substantial research is being carried out within the eld of
energy in order to nd alternative fuels to replace gasoline and
diesel. The optimal solution would be an alternative which is
equivalent to the conventional fuels, i.e. compatible with the infrastructure as we know it, but also a fuel which is sustainable and will
decrease the CO2 emission and thereby decrease the environmental
man-made footprint [6].
Biomass derived fuels could be the prospective fuel of tomorrow as these can be produced within a relatively short cycle and
are considered benign for the environment [4,7]. So far rst generation bio-fuels (bio-ethanol and biodiesel) have been implemented
in different parts of the World [8,9]. However, these technologies
rely on food grade biomass; rst generation bio-ethanol is produced
from the fermentation of sugar or starch and biodiesel is produced
on the basis of fats [1012]. This is a problem as the requirement
for food around the World is a constraint and the energy efciency
per unit land of the required crops is relatively low (compared to
energy crops) [13]. For this reason new research focuses on developing second generation bio-fuels, which can be produced from
other biomass sources such as agricultural waste, wood, etc. Table 1
summarizes different paths for producing fuels from biomass and
display which type of biomass source is required, showing that a
series of paths exists which can utilise any source of biomass.
Of the second generation biofuel paths, a lot of efforts are
presently spent on the biomass to liquid route via syngas to optimize the efciency [1417] and also synthesis of higher alcohols
from syngas or hydrocarbons from methanol [16,1822]. As an
alternative, the estimated production prices shown in Table 1 indicate that HDO constitute a feasible route for the production of
synthetic fuels. The competiveness of this route is achieved due
to a good economy when using bio-oil as platform chemical (lower
transport cost for large scale plants) and the exibility with respect
to the biomass feed [10,2325]. Furthermore this route also constitute a path to fuels applicable in the current infrastructure [10].
Jointly, HDO and zeolite cracking are referred to as catalytic
bio-oil upgrading and these could become routes for production of
second generation bio-fuels in the future, but both routes are still
far from industrial application. This review will give an overview
on the present status of the two processes and also discuss which
aspects need further elucidation. Each route will be considered
independently. Aspects of operating conditions, choice of catalyst,
reaction mechanisms, and deactivation mechanisms will be discussed. These considerations will be used to give an overview of the
11
12
13
14
16
17
17
17
Table 1
Overview of potential routes for production of renewable fuels from biomass. The
prices are based on the lower heating value (LHV). Biomass as feed implies high
exibility with respect to feed source.
Technology
Feed
Platform chemical
Price [$/toea ]
HDO
Zeolite cracking
FischerTropsch
H2
Methanol
Higher alcohols
Bio-ethanol
Bio-ethanol
Bio-ethanol
Biodiesel
Biodiesel
Gasoline
Biomass
Biomass
Biomass
Biomass
Biomass
Biomass
Sugar cane
Corn
Biomass
Canola oil
Palm oil
Crude oil
Bio-oil
Bio-oil
Syngas
Syngas
Syngas
Syngas
740b
8401134c
378714d, e
546588f
13021512g
369922h
11071475i
14752029j
5861171k
586937l
1046m
Table 2
Bio-oil composition in wt% on the basis of different biomass sources and production methods.
Corn cobs
Corn stover
Pine
Softwood
Hardwood
Ref.
T [ C]
Reactor
[45]
500
Fluidized bed
[45]
500
Fluidized bed
[50,31]
520
Transport bed
[195]
500
Rotating bed
[195]
Transport bed
Water
Aldehydes
Acids
Carbohydrates
Phenolics
Furan etc.
Alcohols
Ketones
Unclassied
25
1
6
5
4
2
0
11
46
9
4
6
12
2
1
0
7
57
24
7
4
34
15
3
2
4
5
2932
117
310
37
23
02
01
24
2457
2021
05
57
34
23
01
04
78
4758
Table 3
Comparison between bio-oil and crude oil. Data are from Refs. [10,11,28].
Water [wt%]
pH
[kg/l]
50 C [cP]
HHV [MJ/kg]
C [wt%]
O [wt%]
H [wt%]
S [wt%]
N [wt%]
Ash [wt%]
Bio-oil
Crude oil
1530
2.83.8
1.051.25
40100
1619
5565
2840
57
<0.05
<0.4
<0.2
0.1
0.86
180
44
8386
<1
1114
<4
<1
0.1
(1)
(2)
Yoil =
moil
mfeed
100
(3)
Fig. 1. Examples of reactions associated with catalytic bio-oil upgrading. The gure is drawn on the basis of information from Refs. [51,53].
DOD =
wt%O in product
wtO in feed
100
(4)
Here Yoil is the yield of oil, moil is the mass of produced oil, mfeed
is the mass of the feed, DOD is the degree of deoxygenation, and
wt%O is the weight percent of oxygen in the oil. The two parameters together can give a rough overview of the extent of reaction,
as the oil yield describes the selectivity toward an oil product and
the degree of deoxygenation describes how effective the oxygen
removal has been and therefore indicates the quality of the produced oil. However, separately the parameters are less descriptive,
for it can be seen that a 100% yield can be achieved in the case
of no reaction. Furthermore, none of the parameters relate to the
removal of specic troublesome species and these would have to
be analyzed for in detail.
Table 4
Overview of catalysts investigated for catalytic upgrading of bio-oil.
Catalyst
Hydrodeoxygenation
CoMoS2 /Al2 O3
CoMoS2 /Al2 O3
NiMoS2 /Al2 O3
NiMoS2 /Al2 O3
Pd/C
Pd/C
Pd/ZrO2
Pt/Al2 O3 /SiO2
Pt/ZrO2
Rh/ZrO2
Ru/Al2 O3
Ru/C
Ru/C
Ru/TiO2
Zeolite cracking
GaHZSM-5
H-mordenite
HY
HZSM-5
HZSM-5
MgAPO-36
SAPO-11
SAPO-5
ZnHZSM-5
a
b
Setup
Feed
Time [h]
Batch
Continuous
Batch
Continuous
Batch
Continuous
Batch
Continuous
Batch
Batch
Batch
Continuous
Batch
Batch
Bio-oil
Bio-oil
Bio-oil
Bio-oil
Bio-oil
Bio-oil
Guaiacol
Bio-oil
Guaiacol
Guaiacol
Bio-oil
Bio-oil
Bio-oil
Bio-oil
4
4a
4
0.5a
4
4b
3
0.5a
3
3
4
0.2a
4
4
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Continuous
Bio-oil
Bio-oil
Bio-oil
Bio-oil
Bio-oil
Bio-oil
Bio-oil
Bio-oil
Bio-oil
0.32a
0.56a
0.28a
0.32a
0.91a
0.28a
0.28a
0.28a
0.32a
P [bar]
200
300
200
85
200
140
80
85
80
80
200
230
200
200
1
1
1
1
1
1
1
1
1
T [ C]
350
370
350
400
350
340
300
400
300
300
350
350400
350
350
380
330
330
380
500
370
370
370
380
DOD [%]
O/C
H/C
Yoil [wt%]
Ref.
81
100
74
28
85
64
45
78
73
86
77
0.8
0.0
0.1
0.7
0.1
0.1
0.2
0.0
0.4
0.1
0.8
1.0
1.3
1.8
1.5
1.6
1.5
1.3
1.5
1.2
1.2
1.5
1.5
1.7
26
33
28
84
65
48
81
36
38
53
67
[53]
[70]
[53]
[119]
[53]
[61]
[66]
[119]
[66]
[66]
[53]
[11]
[53]
[53]
50
53
0.2
0.2
1.2
1.2
18
17
28
24
12
16
20
22
19
[130]
[145]
[145]
[130]
[127]
[194]
[194]
[194]
[130]
(5)
Table 5
Activation energy (EA ), iso-reactive temperature (Tiso ), and hydrogen consumption for the deoxygenation of different functional groups or molecules over a
CoMoS2 /Al2 O3 catalyst. Data are obtained from Grange et al. [23].
Molecule/group
EA [kJ/mol]
TIso [ C]
Hydrogen consumption
Ketone
Carboxylic acid
Methoxy phenol
4-Methylphenol
2-Ethylphenol
Dibenzofuran
50
109
113
141
150
143
203
283
301
340
367
417
2 H2 /group
3 H2 /group
6 H2 /molecule
4 H2 /molecule
4 H2 /molecule
8 H2 /molecule
reactor at 140 bar. Here it was found that the oil yield decreased
from 75% to 56% when increasing the temperature from 310 C to
360 C. This was accompanied by an increase in the gas yield by
a factor of 3. The degree of deoxygenation increased from 65% at
310 C to 70% at 340 C. Above 340 C the degree of deoxygenation
did not increase further, but instead extensive cracking took place
rather than deoxygenation.
The observations of Elliott et al. [61] are due to the reactivity of
the different types of functional groups in the bio-oil [23,67]. Table 5
summarizes activation energies, iso-reactivity temperatures (the
temperature required for a reaction to take place), and hydrogen
consumption for different functional groups and molecules over a
CoMoS2 /Al2 O3 catalyst. On this catalyst the activation energy for
deoxygenation of ketones is relatively low, so these molecules can
be deoxygenated at temperatures close to 200 C. However, for the
more complex bound or sterically hindered oxygen, as in furans
or ortho substituted phenols, a signicantly higher temperature is
required for the reaction to proceed. On this basis the apparent
reactivity of different compounds has been summarized as [27]:
alcohol > ketone > alkylether > carboxylic acid
(6)
Here CH1.47 O0.11 is the organic phase of the product and CH3.02 O1.09
is the aqueous phase of the product. Some oxygen is incorporated
in the hydrocarbons of the organic phase, but the O/C ratio is signicantly lower in the hydrotreated organic phase (0.11) compared
to the pyrolysis oil (0.56). In the aqueous phase a higher O/C ratio
than in the parent oil is seen [11].
Regarding operating conditions, a high pressure is generally
used, which has been reported in the range from 75 to 300 bar
in the literature [31,60,61]. Patent literature describes operating
pressures in the range of 10120 bar [62,63]. The high pressure has
been described as ensuring a higher solubility of hydrogen in the
oil and thereby a higher availability of hydrogen in the vicinity of
the catalyst. This increases the reaction rate and further decreases
coking in the reactor [11,64]. Elliott et al. [61] used hydrogen in an
excess of 35420 mol H2 per kg bio-oil, compared to a requirement
of around 25 mol/kg for complete deoxygenation [11].
High degrees of deoxygenation are favoured by high residence
times [31]. In a continuous ow reactor, Elliott et al. [61] showed
that the oxygen content of the upgraded oil decreased from 21 wt%
to 10 wt% when decreasing the LHSV from 0.70 h1 to 0.25 h1 over
a Pd/C catalyst at 140 bar and 340 C. In general LHSV should be in
the order of 0.11.5 h1 [63]. This residence time is in analogy to
batch reactor tests, which usually are carried out over timeframes
of 34 h [53,65,66].
HDO is normally carried out at temperatures between 250 and
450 C [11,57]. As the reaction is exothermic and calculations of
the equilibrium predicts potential full conversion of representative
model compounds up to at least 600 C, it appears that the choice of
operating temperature should mainly be based on kinetic aspects.
The effect of temperature was investigated by Elliott and Hart [61]
for HDO of wood based bio-oil over a Pd/C catalyst in a xed bed
This development was presumed to be due to the different reactivity values of the compounds in the bio-oil. Highly reactive
oxygenates, like ketones, are easily converted with low hydrogen
consumption, but some oxygen is bound in the more stable compounds. Thus, the more complex molecules are accompanied by an
initial hydrogenation/saturation of the molecule and therefore the
hydrogen consumption exceeds the stoichiometric prediction at
the high degrees of deoxygenation [27]. These tendencies are also
illustrated in Table 5. Obviously, the hydrogen requirement for
HDO of a ketone is signicantly lower than that for a furan. Overall
this means that in order to achieve 50% deoxygenation (ca. 25 wt%
oxygen in the upgraded oil) 8 mol H2 per kg bio-oil is required
according to Fig. 2. In contrast, complete deoxygenation (and
accompanied saturation) has a predicted hydrogen requirement of
ca. 25 mol/kg, i.e. an increase by a factor of ca. 3.
The discussion above shows that the use of hydrogen for upgrading bio-oil has two effects with respect to the mechanism: removing
oxygen and saturating double bounds. This results in decreased
O/C ratios and increased H/C ratios, both of which increase the fuel
grade of the oil by increasing the heating value (HV). Mercader et al.
[60] found that the higher heating value (HHV) of the nal product
Fig. 4. Proposed mechanism of HDO of 2-ethylphenol over a CoMoS2 catalyst. The dotted circle indicates the catalytically active vacancy site. The gure is drawn on the
basis of information from Romero et al. [85].
For the mechanism to work, it is a necessity that the oxygen group formed on the metal site from the deoxygenation step
is eliminated as water. During prolonged operation it has been
observed that a decrease in activity can occur due to transformation of the catalyst from a sulphide form toward an oxide form. In
order to avoid this, it has been found that co-feeding H2 S to the
system will regenerate the sulphide sites and stabilize the catalyst
[79,84,87,88]. However, the study of Senol et al. [87,88] showed that
trace amounts of thiols and sulphides was formed during the HDO
of 3 wt% methyl heptanoate in m-xylene at 15 bar and 250 C in a
xed bed reactor with CoMoS2 /Al2 O3 co-fed with up to 1000 ppm
H2 S. Thus, these studies indicate that sulphur contamination of the
otherwise sulphur free oil can occur when using sulphide type catalysts. An interesting perspective in this is that CoMoS2 /Al2 O3 is
used as industrial HDS catalyst where it removes sulphur from oils
down to a level of a few ppm [89]. On the other hand, Christensen
et al. [19] showed that, when synthesizing higher alcohols from
synthesisgas with CoMoS2 /C co-fed with H2 S, thiols and suldes
were produced as well. Thus, the inuence of the sulphur on this
catalyst is difcult to evaluate and needs further attention.
On the basis of density functional theory (DFT) calculations,
Moberg et al. [90] proposed MoO3 as catalyst for HDO. These calculations showed that the deoxygenation on MoO3 occur similar
to the path in Fig. 4, i.e. chemisorption on a coordinatevely unsaturated metal site, proton donation, and desorption. For both oxide
and sulphide type catalysts the activity relies on the presence
of acid sites. The initial chemisorption step is a Lewis acid/base
interaction, where the oxygen lone pair of the target molecule is
attracted to the unsaturated metal site. For this reason it can be
speculated that the reactivity of the system must partly rely on
the availability and strength of the Lewis acid sites on the catalyst.
Gervasini and Auroux [91] reported that the relative Lewis acid site
surface concentration on different oxides are:
Cr2 O3 > WO3 > Nb2 O5 > Ta2 O5 > V2 O5 MoO3
(8)
(9)
(10)
Fig. 5. HDO mechanism over transition metal catalysts. The mechanism drawn on
the basis of information from Refs. [95,96].
(11)
Fig. 6 shows the results from another study of noble metal catalysts by Wildschut et al. [53,104]. Here Ru/C, Pd/C, and Pt/C were
investigated for HDO of beech bio-oil in a batch reactor at 350 C
and 200 bar over 4 h. Ru/C and Pd/C appeared to be good catalysts
for the process as they displayed high degrees of deoxygenation
and high oil yields, relative to CoMoS2 /Al2 O3 and NiMoS2 /Al2 O3
as benchmarks.
Through experiments in a batch reactor setup with synthetic
bio-oil (mixture of compounds representative of the real bio-oil) at
350 C and ca. 10 bar of nitrogen, Fisk et al. [105] found that Pt/Al2 O3
displayed catalytic activity for both HDO and steam reforming and
therefore could produce H2 in situ. This approach is attractive as the
expense for hydrogen supply is considered as one of the disadvantages of the HDO technology. However, the catalyst was reported
to suffer from signicant deactivation due to carbon formation.
Fig. 6. Comparison of Ru/C, Pd/C, Pt/C, CoMoS2 /Al2 O3 and NiMoS2 /Al2 O3 as catalysts for HDO, evaluated on the basis of the degree of deoxygenation and oil yield.
Experiments were performed with beech bio-oil in a batch reactor at 350 C and
200 bar over 4 h. Data are from Wildschut et al. [53,104].
To summarize, the noble metal catalysts Ru, Rh, Pd, and possibly
also Pt appear to be potential catalysts for the HDO synthesis, but
the high price of the metals make them unattractive.
As alternatives to the noble metal catalysts a series of investigations of base metal catalysts have been performed, as the
prices of these metals are signicantly lower [106]. Yakovlev et al.
[98] investigated nickel based catalysts for HDO of anisole in
a xed bed reactor at temperatures in the range from 250 to
400 C and pressures in the range from 5 to 20 bar. In Fig. 7 the
results of these experiments are shown, where it can be seen that
specically NiCu had the potential to completely eliminate the
oxygen content in anisole. Unfortunately, this comparison only
gives a vague idea about how the nickel based catalysts compare
to other catalysts. Quantication of the activity and afnity for
carbon formation of these catalysts relative to noble metal catalysts such as Ru/C and Pd/C or relative to CoMoS2 would be
interesting.
Zhao et al. [107] measured the activity for HDO in a xed bed
reactor where a hydrogen/nitrogen gas was saturated with gaseous
guaiacol (H2 /guaiacol molar ratio of 33) over phosphide catalysts
supported on SiO2 at atmospheric pressure and 300 C. On this basis
the following relative activity was found:
Ni2 P/SiO2 > Co2 P/SiO2 > Fe2 P/SiO2 > WP/SiO2 > MoP/SiO2
(12)
All the catalysts were found less active than Pd/Al2 O3 , but more
stable than CoMoS2 /Al2 O3 . Thus, the attractiveness of these cat-
Fig. 7. Performance of nickel based catalysts for HDO. HDO degree is the ratio
between the concentrations of oxygen free product relative to all products. Experiments performed with anisole in a xed bed reactor at 300 C and 10 bar. Data from
Yakovlev et al. [98].
4.1.3. Supports
The choice of carrier material is an important aspect of catalyst
formulation for HDO [98].
Al2 O3 has been shown to be an unsuitable support, as it in the
presence of larger amounts of water it will convert to boemite
(AlO(OH)) [11,26,111]. An investigation of Laurent and Delmon
[111] on NiMoS2 /-Al2 O3 showed that the formation of boemite
resulted in the oxidation of nickel on the catalyst. These nickel
oxides were inactive with respect to HDO and could further block
other Mo or Ni sites on the catalyst. By treating the catalyst in a
mixture of dodecane and water for 60 h, a decrease by two thirds of
the activity was seen relative to a case where the catalyst had been
treated in dodecane alone [26,111].
Additionally, Popov et al. [112] found that 2/3 of alumina was
covered with phenolic species when saturating it at 400 C in a
phenol/argon ow. The observed surface species were believed to
be potential carbon precursors, indicating that a high afnity for
carbon formation exists on this type of support. The high surface
coverage was linked to the relative high acidity of Al2 O3 .
As an alternative to Al2 O3 , carbon has been found to be a more
promising support [53,94,113115]. The neutral nature of carbon
is advantageous, as this gives a lower tendency for carbon formation compared to Al2 O3 [94,114]. Also SiO2 has been indicated as a
prospective support for HDO as it, like carbon, has a general neutral nature and therefore has a relatively low afnity for carbon
formation [107]. Popov et al. [112] showed that the concentration
of adsorbed phenol species on SiO2 was only 12% relative to the
concentration found on Al2 O3 at 400 C. SiO2 only interacted with
phenol through hydrogen bonds, but on Al2 O3 dissociation of phenol to more strongly adsorbed surface species on the acid sites was
observed [116].
ZrO2 and CeO2 have also been identied as potential carrier
materials for the synthesis. ZrO2 has some acidic character, but signicantly less than Al2 O3 [117]. ZrO2 and CeO2 are thought to have
the potential to activate oxy-compounds on their surface, as shown
in Fig. 5, and thereby increase activity. Thus, they seem attractive
in the formulation of new catalysts, see also Fig. 7 [66,98,117,118].
Overall two aspects should be considered in the choice of support. On one hand the afnity for carbon formation should be
low, which to some extent is correlated to the acidity (which
should be low). Secondly, it should have the ability to activate oxycompounds to facilitate sufcient activity. The latter is especially
important when dealing with base metal catalysts, as discussed in
Section 4.1.2.
dwoxy
m
= k woxy
Pn
dZ
(13)
Here woxy is the mass of oxygen in the product relative to the oxygen in the raw pyrolysis oil, Z is the axial position in the reactor, k
is the rate constant given by an Arrhenius expression, P is the total
pressure (mainly H2 ), m is the reaction order for the oxygen, and
n is the reaction order for the total pressure. In the study it was
assumed that all three types of catalyst could be described by a
rst order dependency with respect to the oxygen in the pyrolysis
oil (i.e. m = 1). On this basis the pressure dependency and activation
energy could be found, which are summarized in Table 6. Generally
a positive effect of an increased pressure was reported as n was in
the range from 0.3 to 1. The activation energies were found in the
range from 45.5 to 71.4 kJ/mol, with Pt/Al2 O3 /SiO2 having the lowest activation energy. The lower activation energy for the Pt catalyst
was in agreement with an observed higher degree of deoxygenation
compared to the two other. The results of this study are interesting, however, the rate term of Eq. (13) has a non-fundamental form
as the use of mass related concentrations and especially using the
axial position in the reactor as time dependency makes the term
very specic for the system used. Thus, correlating the results to
other systems could be difcult. Furthermore, the assumption of a
general rst order dependency for woxy is a very rough assumption
when developing a kinetic model.
A similar approach to that of Sheu et al. [119] was made by SuPing et al. [67], where CoMoS2 /Al2 O3 was investigated for HDO of
bio-oil in a batch reactor between 360 and 390 C. Here a general
low dependency on the hydrogen partial pressure was found over
a pressure interval from 15 bar to 30 bar, so it was chosen to omit
the pressure dependency. This led to the expression:
dC oxy
2.3
= k Coxy
dt
(14)
Table 6
Kinetic parameters for the kinetic model in Eq. (13) of different catalysts. Experiments performed in a packed bed reactor between ca. 300400 C and 45105 bar.
Data are from Sheu et al. [119].
Catalyst
Ea [kJ/mol]]
Pt/Al2 O3 /SiO2
CoMoS2 /Al2 O3
NiMoS2 /Al2 O3
1
1
1
1.0
0.3
0.5
45.5 3.2
71.4 14.6
61.7 7.1
dC Phe
k1 KAds CPhe + k2 KAds CPhe
=
d
(1 + CPhe,0 KAds CPhe )2
(15)
Here CPhe is the phenol concentration, CPhe,0 the initial phenol concentration, KAds the equilibrium constant for adsorption of phenol
on the catalyst, the residence time, and k1 and k2 rate constants for
respectively a direct deoxygenation path (cf. Eq. (1)) and a hydrogenation path (cf. Eq. (2)). It is apparent that in order to describe
HDO in detail all contributing reaction paths have to be regarded.
This is possible when a single molecule is investigated. However,
expanding this analysis to a bio-oil reactant will be too comprehensive, as all reaction paths will have to be considered.
Overall it can be concluded that describing the kinetics of HDO
is complex due to the nature of a real bio-oil feed.
4.3. Deactivation
A pronounced problem in HDO is deactivation. This can occur
through poisoning by nitrogen species or water, sintering of the
catalyst, metal deposition (specically alkali metals), or coking [59].
The extent of these phenomena is dependent on the catalyst, but
carbon deposition has proven to be a general problem and the main
path of catalyst deactivation [120].
Carbon is principally formed through polymerization and
polycondensation reactions on the catalytic surface, forming polyaromatic species. This results in the blockage of the active sites
on the catalysts [120]. Specically for CoMoS2 /Al2 O3 , it has been
shown that carbon builds up quickly due to strong adsorption of
polyaromatic species. These ll up the pore volume of the catalyst during the start up of the system. In a study of Fonseca et al.
[121,122], it was reported that about one third of the total pore volume of a CoMoS2 /Al2 O3 catalyst was occupied with carbon during
this initial carbon deposition stage and hereafter a steady state was
observed where further carbon deposition was limited [120].
The rates of the carbon forming reactions are to a large extent
controlled by the feed to the system, but process conditions also
play an important role. With respect to hydrocarbon feeds, alkenes
and aromatics have been reported as having the largest afnity
for carbon formation, due to a signicantly stronger interaction
with the catalytic surface relative to saturated hydrocarbons. The
stronger binding to the surface will entail that the conversion of
the hydrocarbons to carbon is more likely. For oxygen containing
hydrocarbons it has been identied that compounds with more
than one oxygen atom appears to have a higher afnity for carbon formation by polymerization reactions on the catalysts surfaces
[120].
Coking increases with increasing acidity of the catalyst; inuenced by both Lewis and Brnsted acid sites. The principle function
of Lewis acid sites is to bind species to the catalyst surface. Brnsted
sites function by donating protons to the compounds of relevance,
forming carbocations which are believed to be responsible for coking [120]. This constitute a problem as acid sites are also required
in the mechanism of HDO (cf. Fig. 4). Furthermore, it has been
found that the presence of organic acids (as acetic acid) in the feed
will increase the afnity for carbon formation, as this catalyses the
thermal degradation path [104].
In order to minimize carbon formation, measures can be taken in
the choice of operating parameters. Hydrogen has been identied as
efciently decreasing the carbon formation on CoMoS2 /Al2 O3 as it
will convert carbon precursors into stable molecules by saturating
surface adsorbed species, as for example alkenes [120,123].
10
Fig. 8. Yields of oil and gas compared to the elemental oxygen content in the oil from
a zeolite cracking process as a function of temperature. Experiments were performed
with a HZSM-5 catalyst in a xed bed reactor for bio-oil treatment. Yields are given
relative to the initial biomass feed. Data are from Williams and Horne [127].
(16)
(17)
H 2O 3N 2S
C
(18)
11
Fig. 9. Dehydration mechanism for ethanol over zeolites. The left route is the decomposition route and the right route is the bimolecular monomer dehydration. The
mechanism is drawn on the basis of information from Chiand and Bhan [139].
> H-mordenite(6.7 A)
> HY(7.4 A)
HZSM-5(5.4 A)
> silicalite(5.4 A)
> silica-alumina(31.5 A)
(19)
With the number in the parentheses being the average pore sizes
of the zeolites. Practically, silicalite does not contain any acid sites
as it is a polymorph structure of Si. In comparison, HZSM-5 is rich
in both Lewis and Brnsted acid sites. The above correlation therefore shows that the activity of zeolite cracking catalysts are highly
dependent on the availability of acid sites [140].
Fig. 10. Reaction network for the kinetic model described in Eqs. (20)(26).
12
Volatiles :
dC NV
0.9
r1
c1
= kNV CB kCr CNV
kR1 CNV
kC1 CNV
dt
(20)
dC V
g
0.9
= kV CB + kCr CNV
kOil CVo kGas CV
dt
kAqua CVa kR2 CVr2 kC2 CVc2
Oil :
dC Oil
= kOil CVo
dt
Aqueous :
Gas :
dC Aqua
= kAqua CVa
dt
dC Gas
g
= kGas CV
dt
(21)
(22)
(23)
(24)
Carbon :
dC C
c1
= kC1 CNV
+ kC2 CVc2
dt
(25)
Residue :
dC R
r1
+ kR2 CVr2
= kR1 CNV
dt
(26)
Fig. 11. Fit between a kinetic model for zeolite cracking of bio-oil and experimental data. Experiments were performed in a xed bed reactor with aspen bio-oil as
feed and HZSM-5 as catalyst. The gure is reproduced from Adjaye and Bakhshi
[52].
5.3. Deactivation
As for HDO, carbon deposition and thereby catalyst deactivation
constitute a pronounced problem in zeolite cracking.
In zeolite cracking, carbon is principally formed through polymerization and polycondensation reactions, such formation results
in the blockage of the pores in the zeolites [143,148]. Guo et al.
[148] investigated the carbon precursors formed during operation
of bio-oil over HZSM-5 and found that deactivation was caused by
an initial build-up of high molecular weight compounds, primarily
having aromatic structures. These species formed in the inner part
of the zeolites and then expanded, resulting in the deactivation of
the catalyst.
Gayubo et al. [147] investigated the carbon formed on HZSM-5
during operation with synthetic bio-oil in a xed bed reactor at
400450 C with temperature programmed oxidation (TPO) and
found two types of carbon: thermal carbon and catalytic carbon.
The thermal carbon was described as equivalent to the depositions
on the reactor walls and this was only found in the macropores
of the catalyst. The catalytic carbon was found in the micropores
of the zeolites and was ascribed to dehydrogenation, condensation, and hydrogen transfer reactions. This was found to have a
lower hydrogen content compared to the thermal carbon [147,155].
In the TPO, the thermal carbon was removed at lower temperatures (450480 C) compared to the catalytic carbon, which was
removed at 520550 C. These observations were assumed due to
the catalytic carbon being steric hindered, deposited in the micropores, strongly bound to the acidic sides of the zeolite, and less
reactive due to the hydrogen decient nature. The conclusion of
the study was that the catalytic carbon was the principal source
of deactivation, as this resulted in blockage of the internal acidic
sites of the catalyst, but thermal carbon also contributed to the
deactivation.
The study of Huang et al. [143] described that acid sites played
a signicant role in the formation of carbon on the catalysts. Proton donation from these was reported as a source for hydrocarbon
cations. These were described as stabilized on the deprotonated
basic framework of the zeolite, which facilitated potential for cracking and aromatization reactions, leading to carbon.
Summarizing, it becomes apparent that carbon forming reactions are driven by the presence of acid sites on the catalyst leading
to poly (aromatic) carbon species. The acid sites are therefore the
essential part of the mechanism for both the deoxygenating reactions (cf. Section 5.1) and the deactivating mechanisms.
Trying to decrease the extent of carbon formation on the catalyst, Zhu et al. [154] investigated co-feeding of hydrogen to anisole
over HZSM-5 in a xed bed reactor at 400 C. This showed that
the presence of hydrogen only decreased the carbon formation
slightly. It was suggested that the hydrogen had the afnity to react
with adsorbed carbenium ions to form parafns, but apparently the
effect of this was not sufcient to increase the catalyst lifetime in
any signicant degree. Ausavasukhi et al. [156] reached a similar
conclusion in another study of deoxygenation of benzaldehyde over
HZSM-5, where it was described that the presence of hydrogen did
not inuence the conversion. However, a shift in selectivity was
observed as an increase in toluene production was observed with
H2 , which was ascribed to hydrogenation/hydrogenolysis reactions
taking place.
In a study of Peralta et al. [157] co-feeding of hydrogen was
investigated for cracking of benzaldehyde over NaX zeolites with
and without Cs at 475 C. The observed conversion as a function of
time on stream is shown in Fig. 12. Comparing the performance of
CsNaX and NaX in hydrogen shows that the stability of the CsNaX
catalyst was signicantly higher as the conversion of this catalyst
only decreased by ca. 10% after 8 h, compared to a drop of ca. 75% for
NaX. However, as CsNaX has an initial conversion of 100% this drop
Fig. 12. Stability of CsNaX and NaX zeolites for cracking of benzaldehyde with either
H2 or He as carrier gas. Experiments were performed in a xed bed reactor at 475 C.
Data are from Peralta et al. [157].
13
cycles, relative to the fresh catalyst. The fresh catalyst produced oil
with 21 wt% oxygen, but after 5 regenerations this had increased
to 30 wt%. It was concluded that this was due to a decrease in the
amount of exposed active sites on the catalyst.
At elevated steam concentrations it has been found that aluminosilicates can undergo dealumination where the tetrahedral
alumina in the zeolite frame is converted into so called partially
distorted octahedral alumina atoms. These can diffuse to the outer
surface of the zeolite where they are converted into octahedrally
coordinated alumina atoms, which are not acidic. Overall this process will entail that the availability of acidic sites in the zeolite
will decrease during prolonged exposure to elevated steam concentrations [159,161]. As Vitolo et al. [141] observed a decrease in
the availability of acid sites in the zeolite used for bio-oil upgrading and because bio-oil has a general high water content, it could
be speculated that dealumination is inevitably occurring during
zeolite cracking of bio-oil and thus regeneration cannot be done.
Overall, the work of Vitolo et al. [141] and Guo et al. [130] are
in analogy with traditional FCC where air is used to remove carbon
depositions on the catalyst [162], but it appears that this method
can not be applied to zeolite cracking of bio-oils. Thus, new strategies are required.
6. General aspects
The grade of the fuels produced from upgrading bio-oil is an
important aspect to consider, but depending on the process conditions different product compositions will be achieved. Table 7
illustrates what can be expected for the compositions and the characteristics between raw pyrolysis oil, HDO oil, zeolite cracking oil,
and crude oil (as a benchmark).
Comparing bio-oil to HDO and zeolite cracking oil, it is seen that
the oxygen content after HDO and zeolite cracking is decreased. In
HDO a drop to <5 wt% is seen, where zeolite cracking only decreases
the oxygen content to 1324 wt%. Therefore a larger increase in the
HHV is seen through HDO compared to zeolite cracking. Furthermore, the viscosity at 50 C (50 C ) of the HDO oil is seen to decrease,
which improves ow characteristics and is advantageous in further
processing. The decrease in the oxygen content also affects the pH
value of the oil, as this increases from ca. 3 to about 6 in HDO, i.e.
Table 7
Comparison of characteristics of bio-oil, catalytically upgraded bio-oil, and crude
oil.
Upgraded bio-oil
YOil [wt%]
YWaterphase [wt%]
YGas [wt%]
YCarbon [wt%]
Oil characteristics
Water [wt%]
pH
[kg/l]
50 C [cP]
HHV [MJ/kg]
C [wt%]
O [wt%]
H [wt%]
S [wt%]
N [wt%]
Ash [wt%]
H/C
O/C
a
b
c
d
e
Bio-oila
HDOb
Zeolite crackingc
Crude oild
100
2165
1349
315
426
1228
2428
613
2639
1530
2.83.8
1.051.25
40100
1619
5565
2840
57
<0.05
<0.4
<0.2
0.91.5
0.30.5
1.5
5.8
1.2
15
4245
8589
<5
1014
<0.005
1.32.0
<0.1
2136e
6179
1324
28
0.31.8
0.10.3
0.1
0.86
180
44
8386
<1
1114
<4
<1
0.1
1.52.0
0
14
Table 8
Carbon deposition on different catalysts after operation, given in wt% of total catalyst mass. Data for zeolites in rows 1 and 2 are from Park et al. [144], experiments
performed in a packed bed reactor at 500 C over a period of 1 h with pine bio-oil.
Data for HDO catalysts in rows 3 and 4 are from Gutierrez et al. [66], experiments
performed in a batch reactor at 300 C over a period of 4 h with guaiacol.
Catalyst
Carbon [wt%]
HZSM-5
Meso-MFI
CoMoS2 /Al2 O3
Rh/ZrO2
13.6
21.3
6.7
1.8
Table 9
Oil composition on a water-free basis in mol% through the bio-oil upgrading process
as specied by Elliott et al. [26]. The bio-oil was a mixed wood bio-oil. HDO was performed at 340 C, 138 bar and a LHSV of 0.25 with a Pd/C catalyst. Hydrocracking was
performed at 405 C, 103 bar and a LHSV of 0.2 with a conventional hydrocracking
catalyst.
Ketones/aldehydes
Alkanes
Guaiacols etc.
Phenolics
Alcohols
Aromatics
Acids/esters
Furans etc.
Unknown
Bio-oil
HDO oil
Hydrocracked oil
13.77
0
34.17
10.27
3.5
0
19.78
11.68
6.83
25.08
4.45
10.27
18.55
5.29
0.87
25.21
6.84
3.44
0
82.85
0
0
0
11.53
0
0
5.62
15
Fig. 13. Overall ow sheet for the production of bio-fuels on the basis of catalytic upgrading of bio-oil. The gure is based on information from Jones et al. [167].
catalyst. This should take place between 200 and 300 C and can
be carried out both with and without the presence of hydrogen.
This will prompt the reaction and stabilization of some of the most
reactive compounds in the feed and thereby lower the afnity for
carbon formation in downstream processes [11,75,159,164,167].
After the thermal treatment the actual HDO synthesis is prompted,
producing oils equivalent to the descriptions of Table 7.
The HDO oil is processed by an initial distillation to separate light
and heavy oil. The heavy oil fraction is further processed through
cracking, which here is illustrated by FCC, but also could be hydrocracking. The cracked oil fraction is hereafter joined with the light
oil fraction again. Finally, distillation of the light oil is performed to
separate gasoline, diesel, etc.
Off-gasses from the HDO and the FCC should be utilised in the
hydrogen production. However, these are not sufcient to produce
the required amount of hydrogen for the synthesis, instead additional bio-oil (or another feed) should be supplied to the plant [167].
In the ow sheet of Fig. 13, steam reforming is shown simplied
as a single step followed by hydrogen separation through pressure
swing adsorption (PSA). In reality this step is more complex, as heat
recovery, feed pre-treatment, and water-gas-shift all would have
to be incorporated in such a section, but these details are outside
the scope of this study, readers should instead consult references
[168171]. If hydrogen is supplied from steam reforming of bio-oil,
as indicated in Fig. 13, it would result in a decrease in the fuel production from a given amount of bio-oil by about one third [167].
In the future it is believed that the hydrogen could be supplied
through hydrolysis with energy generation on the basis of solar
or wind energy, when these technologies are mature [57,172,173].
This also offers a route for storage of some of the solar energy.
In between the pyrolysis and the HDO plant a potential stabilization step could be inserted due to the instability of the bio-oil. The
necessity of this step depends on a series of parameters: the time
the bio-oil should be stored, the time required for transport, and the
apparent stability of the specic bio-oil batch. The work of Oasmaa
and Kuoppala [50] indicates that utilisation of the bio-oil should be
done within three months if no measures are taken. Different methods have been suggested in order to achieve increased stability of
bio-oil; one being mixing of the bio-oil with alcohols, which should
decrease the reactivity [49,152,159]. Furthermore a low temperature thermal hydrotreatment (100200 C) has been proposed, as
this will prompt the hydrodeoxygenation and cracking of some of
the most reactive groups [23].
In the design of a catalytic upgrading unit it is relevant to look at
the already well established HDS process, where the usual choice
is a trickle bed reactor [9,120,174,175]. Such a reactor is illustrated
in Fig. 14. This is essentially a packed bed reactor, but operated in
a multiphase regime. In the reactor the reactions occur between
the dissolved gas (hydrogen) and the liquid on the catalytic surface. The liquid ow occurs as both lm and rivulet ow lling
the catalyst pores with liquid [176,177]. The advantages of using a
trickle bed reactor, with respect to the current HDO process, are: the
ow pattern resemblance plug ow behaviour giving high conversions, low catalyst loss, low liquid/solid ratio ensuring low afnity
for homogenous reactions in the oil, relatively low investment
costs, and possibility to operate at high pressure and temperature
[177,175].
The HDO process has been evaluated as being a suitable choice in
the production of sustainable fuels, due to a high carbon efciency
and thereby a high production potential [10,23,173,178]. In an evaluation by Singh et al. [173] it was estimated that the production
capacity on an arable land basis was 3035 MJ fuel/m2 land/year
for pyrolysis of the biomass followed by HDO, combined with gasication of a portion of the biomass for hydrogen production. In
comparison, gasication of biomass followed by FischerTropsch
synthesis was in the same study estimated as having a land utilisation potential in the order of 2126 MJ fuel/m2 land/y. It was further
found that the production of fuels through HDO could be increased
by approximately 50% if the hydrogen was supplied from solar
energy instead of gasication, thus being 50 MJ fuel/m2 land/year.
However, care should be taken with these results, as they are calculated on the basis of assumed achievable process efciencies.
16
Fig. 14. Scheme of a trickle bed reactor. The gure is drawn on the basis of information from Mederos et al. [175].
(27)
of the individual fractions on the basis of detailed kinetic investigations on representative model compounds [190,191]. In order
to describe the kinetics of HDO (and zeolite cracking as well) of
bio-oil an approach similar to this would probably be necessary,
where the division probably should be on the basis of functional
groups.
Further elucidation of HDO in industrial scale is also a request.
Elaboration of why high pressure operation is a necessity and evaluation of potential transport limitations in the system are still
subjects to be treated, they also have been questioned by Venderbosch et al. [11]. Both aspects affect the reactor choice, as the
proposed trickle bed reactor in Section 7 potentially could be
replaced with a better engineering solution.
9. Conclusion and future tasks
Due to the demand for fuels, the increased build-up of CO2 in the
atmosphere, and the general fact that the oil reserves are depleting,
the need of renewable fuels is evident. Biomass derived fuels is in
this context a promising route, being the only renewable carbon
resource with a sufciently short reproduction cycle.
Problems with biomass utilisation are associated with the high
cost of transport due to the low mass and energy density. To circumvent this, local production of bio-oil seems a viable option, being
a more energy dense intermediate for processing of the biomass.
This process is further applicable with all types of biomass. However, the bio-oil suffers from a high oxygen content, rendering it
acidic, instable, immiscible with oil, and giving it a low heating
value. Utilisation of bio-oil therefore requires further processing in
order to use it as a fuel.
Several applications of bio-oil have been suggested. Deoxygenation seems one of the most prospective options, which is a method
to remove the oxygen containing functional groups. Two different
main routes have been proposed for this: HDO and zeolite cracking.
HDO is a high pressure synthesis where oxygen is removed from
the oil through hydrogen treatment. This produces oil with low
oxygen content and a heating value equivalent to crude oil.
Zeolite cracking is performed at atmospheric pressure in the
absence of hydrogen, removing oxygen through cracking reactions.
This is attractive from a process point of view, but it has been found
unfeasible since the product is a low grade fuel and because of a
too high carbon formation (2040 wt%). The latter results in rapid
deactivation of the catalyst.
Overall HDO seems the most promising route for production of
bio-fuels through upgrading of bio-oil and the process has further
been found economically feasible with production prices equivalent to conventional fuels from crude oil, but challenges still exist
within the eld. So far the process has been evaluated in industrial scale to some extent, elucidating which unit operations should
be performed when going from biomass to fuel. However, aspects
of the transport mechanisms in the actual HDO reactor and the
high pressure requirement are still untreated subjects which could
help optimize the process and bring it closer to industrial utilisation. Another great concern within the eld is catalyst formulation.
Much effort has focused around either the CoMoS2 system or
noble metal catalysts, but due to a high afnity for carbon formation, and also due to the high raw material prices for the noble
metals, alternatives are needed. Thus, researchers investigate to
substitute the sulphide catalysts with oxide catalysts and the noble
catalysts with base metal catalysts. The principal requirement to
catalysts are to have a high resistance toward carbon formation
and at the same time have a sufcient activity in hydrodeoxygenation.
Overall the conclusion of this review is that a series of elds still
have to be investigated before HDO can be used in industrial scale.
Future tasks include:
17
Acknowledgements
This work is part of the Combustion and Harmful Emission
Control (CHEC) research centre at The Department of Chemical
and Biochemical Engineering at the Danish University of Denmark
(DTU). The present work is nanced by DTU and The Catalysis for
Sustainable Energy initiative (CASE), funded by the Danish Ministry
of Science, Technology and Innovation.
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